CN106311318A - Oxide and molecular sieve compound catalyst and preparation and application thereof - Google Patents

Oxide and molecular sieve compound catalyst and preparation and application thereof Download PDF

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CN106311318A
CN106311318A CN201610822968.1A CN201610822968A CN106311318A CN 106311318 A CN106311318 A CN 106311318A CN 201610822968 A CN201610822968 A CN 201610822968A CN 106311318 A CN106311318 A CN 106311318A
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ssz
catalyst
molecular sieve
oxide
temperature
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刘庆岭
付振超
刘彩霞
郭铭玉
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/783—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Abstract

The invention relates to an oxide and molecular sieve compound catalyst and preparation and application thereof, and belongs to the technical fields of environmental material, environmental catalysis and environmental protection. The catalyst is prepared by taking Cu-SSZ-13 as a primary active component and manganese oxide and cerium oxide as secondary active components exerting synergistic effect, and an impregnation method is adopted. The catalyst is characterized in that low-temperature activity is greatly improved while good medium-high temperature activity of the Cu-SSZ-13 and N2 selectivity are sustained, light-off temperature is reduced to 80DEG C, and NOx conversion rate higher than 90% is achieved within the temperature range of 100-200DEG C; NH3 is taken as a reducing agent, total gas flow rate is 300ml/min, and airspeed is respectively controlled to be 15000, 50000 and 100000h<1>. The catalyst is suitable for both low-temperature NOx treatment after dust separation and desulfation in stationary-source flue gas treatment and low-temperature NOx treatment of cold-start stage in diesel exhaust treatment.

Description

The composite catalyst of a kind of oxide and molecular sieve and preparation and application
Technical field
The invention belongs to environmentally conscious materials, environmental catalysis and environmental protection technical field, relate to stationary source flue gas and diesel vehicle The purification of nitrogen oxide in tail gas, the molecular sieve after exchanging particularly to ion and the preparation of combination of oxides catalyst structure And application.
Background technology
In the last few years, the research of low-temperature SCR catalyst received significant attention.Low-temperature SCR technique typically refers to react at SCR Catalyst in device, its optimum activity temperature range is even lower at 125-200 DEG C.Industrial, the research and development of low temperature catalyst, After SCR device can being placed on electric precipitation and desulfurization, thus save to enter for meeting the hot conditions of hot industry catalyst The energy consumption that row smoke pre-heating is consumed, can also alleviate the toxic action that catalyst is caused by flue dust simultaneously, and then extend catalysis The life-span of agent；During exhaust gas from diesel vehicle processes, when cold start-up and short distance run, gas temperature is low, it is also desirable to low temperature catalyst.Vapour The new emission control systems of car diesel engine requires that catalyst has greater activity below 200 DEG C, thus reduces in conventional ADS driving NOx emission total amount in cycle.
There is the Cu base small pore molecular sieve catalyst of CHA structure, owing to catalysis activity is high, N2Selectivity is good, heat stability HCs poisoning capability excellent, anti-is strong etc. and receive significant attention, particularly Cu-SSZ-13.Xiao Fengshou seminar utilizes in recent years Cu-TEPA complex utilizes cheap choline chloride conduct as template one-step synthesis Cu-SSZ-13 and Zhang Runduo seminar Template synthesis Cu-SSZ-13 etc. greatly reduces the cost of Cu-SSZ-13, is conducive to its large-scale application.But this catalysis The light-off temperature of agent is higher than 150 DEG C, and the conversion rate of NOx temperature range higher than 80% is 225-400 DEG C, i.e. can't fully meet The demand of low-temperature SCR catalyst.
At numerous oxide-based NH3In-SCR catalyst system, Mn base and Ce base catalyst are due to the low temperature work of its excellence Property and receive much concern.Mn species have abundant variable valence, at NH3-SCR reaction has extremely strong low-temperature oxidation also proper energy Power.Ce species have extremely strong storage oxygen and release oxygen ability, are introduced in NH often as auxiliary agent or second component3-SCR is catalyzed In agent system.The MnO of R T.Yang seminar research and developmentx–CeO2Catalyst, at 120 DEG C, air speed is 42000h-1Under conditions of can Realize NO to convert completely, but N2Selectivity is relatively low, generates more N2O。N2O can damage the ozone layer, and is more difficult to be removed.
Therefore, research and development are applicable to the catalyst of low-temperature zone, it is achieved catalyst at the high activity of low-temperature range and high selectivity, Application and nitrogen oxides overall control for low-temperature SCR catalyst are significant.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the present invention provides a kind of eco-friendly low-temperature denitration to be catalyzed Agent and preparation method thereof, this catalyst all has efficient catalytic to purify the performance of NOx in the range of 125-200 DEG C, can realize low temperature Interval high activity and high selectivity, and nontoxic to the mankind and environment, can be widely applied to stationary source flue gas and exhaust gas from diesel vehicle The purification of middle NOx.
In order to achieve the above object, a kind of oxide of present invention proposition and the composite catalyst of molecular sieve, be with Cu- SSZ-13 is main active component, with manganese oxide and cerium oxide for playing synergistic active component, this composite catalyst Expression formula is Mnx-Cey/ Cu-SSZ-13, wherein: x and y is the molar content 2～8% of catalyst.
Above-mentioned oxide and the preparation method of the composite catalyst of molecular sieve, comprise the following steps:
Step one, use ion exchange or utilize Cu-TEPA to prepare cuprio as template one-step synthesis to divide Sub-sieve catalyst Cu-SSZ-13；
Step 2, infusion process is utilized to prepare composite catalyst Mn-Ce/Cu-SSZ-13:
Take manganese nitrate and cerous nitrate is dissolved in deionized water, the cuprio molecular sieve catalyst Cu-that step one is prepared SSZ-13 adds in this mixed solution, and this pasty mixture is dried overnight, so under the conditions of 100 DEG C by magnetic agitation to pasty state After, it is placed in 550 DEG C of calcining 4h in Muffle furnace, obtains powdery product, MnO in this powdery productx、CeO2, Cu-SSZ-13 Molar content is respectively 2～8%, 2～8%, 90%.
Step 3, powdery product step 2 made sieve obtain at 8～15MPa pressure lower sheetings, 40～60 mesh Composite catalyst Mnx-Cey/ Cu-SSZ-13, wherein, x and y is molar content 2～8%.
Further, oxide, with the step one of the preparation method of the composite catalyst of molecular sieve, uses ion exchange Method prepares cuprio molecular sieve catalyst Cu-SSZ-13, including: the copper salt solution of preparation 0.1mol/L, by molecular sieve H-SSZ-13 Joining in copper salt solution, in oil bath pan, 80 DEG C of constant temperature stirring 2h, then, use deionized water filtration washing, under the conditions of 100 DEG C It is dried 12h；Wherein, described copper salt solution is copper nitrate solution, copper-bath, copper chloride solution, curpic carbonate solution, alkali formula carbon One in acid copper and basic copper sulfate；The silica alumina ratio of described molecular sieve H-SSZ-13 is 13.6.
One of preparation following method of employing of described H-SSZ-13: 1) use N, N, N-trimethyl adamantyl ammonium hydroxide Prepare as template；2) tetraethyl ammonium hydroxide is used to prepare as template；3) tetraethyl ammonium hydroxide and N, N are used, N-trimethyl adamantyl ammonium hydroxide is prepared as mixed templates.
The preparation method of the present invention is with Cu-SSZ-13 as active component, and manganese oxide and cerium oxide are synergistic for playing Secondary active component, uses infusion process to prepare, thus reaches the purpose of effectively catalytic reduction of NOx under cryogenic.That is: by this The composite catalyst of the bright oxide prepared and molecular sieve in ammonia selective catalysis nitrogen oxides reduction reacts, reaction temperature Degree is 50～200 DEG C, and with ammonia as reducing agent, control total gas flow rate is at 300ml/min, and air speed is 15000～100000h-1； It is 90～100% 100-200 DEG C of temperature range purification of nitrogen oxides efficiency.
The present invention compared with prior art, has the following advantages and salience effect:
Use catalysis activity height, N2Selectivity is good, excellent heat stability, Cu-SSZ-13 molecule that anti-HCs poisoning capability is strong Sieve catalyst, as active component, utilizes the Mn oxide and cerium oxide that low-temperature oxidation reproducibility is excellent as secondary activity group Point, by synergism therebetween, it is achieved low-temperature catalytic activity excellence and N2Excellent two advantages of selectivity coexist, thus Under cryogenic NOx is converted to nontoxic N2, reach real purification air；This catalyst is at different space velocities Lower superior activity, both can apply to stationary source denitrating flue gas, met becoming after future denitrification apparatus being placed on dust-removal and desulfurizing Gesture is it can also be used to the purification of NOx in exhaust gas from diesel vehicle, and the research and development for diesel vehicle cold-start phase low temperature catalyst open new way Footpath；
Accompanying drawing explanation
Fig. 1 is that the various combination formulated catalyst recorded in the embodiment of the present invention one and comparative example one to five is in same volume Air speed (15000h-1The conversion ratio of the nitrogen oxides reduction under).
Fig. 2 is that the various combination formulated catalyst recorded in the embodiment of the present invention one and comparative example one to five is in same volume Air speed (15000h-1N under)2Selectivity.
Fig. 3 is the Mn of the different manganese cerium proportionings that the embodiment of the present invention one to four preparesx-Cey/ Cu-SSZ-13 catalyst is in phase Same volume air speed (15000h-1The conversion ratio of the nitrogen oxides reduction under).
Fig. 4 is the Mn of the different manganese cerium proportionings that the embodiment of the present invention one to four preparesx-Cey/ Cu-SSZ-13 catalyst is in phase Same volume air speed (15000h-1N under)2Selectivity.
Fig. 5 is the Mn that the embodiment of the present invention one prepares0.06-Ce0.04The pure Cu-that/Cu-SSZ-13 prepares with comparative example three SSZ-13 catalyst is in different volumes air speed (15000,50000,100000h-1The conversion ratio of the nitrogen oxides reduction under).Its In, air speed is 15000h-1Activity data be labeled as catalyst-1, air speed is 50000h-1Activity data be labeled as catalysis Agent-2, air speed is 100000h-1Activity data be labeled as catalyst-3.
Fig. 6 is the Mn that the embodiment of the present invention one prepares0.06-Ce0.04The pure Cu-that/Cu-SSZ-13 prepares with comparative example three SSZ-13 catalyst is in different volumes air speed (15000,50000,100000h-1N under)2Selectivity.Wherein, air speed is 15000h-1Activity data be labeled as catalyst-1, air speed is 50000h-1Activity data be labeled as catalyst-2, air speed is 100000h-1Activity data be labeled as catalyst-3.
Detailed description of the invention
Tell about the detailed content of the present invention by the following examples, it is provided that embodiment is the convenience in order to understand, be definitely not Limit the present invention.
Embodiment one: preparing the low-temperature denitration catalyst that oxide is compound with molecular sieve, step is as follows:
First, the Cu (NO of 12.08g is taken3)2·3H2O is dissolved in the deionized water of 500mL, the Cu of preparation 0.1mol/L (NO3)2Solution.The H-SSZ-13 that Si/Al is 13.6 is added in copper nitrate solution, 80 DEG C of constant temperature stirring 2h in oil bath pan, will This sample deionized water filtration washing, dries 12h under the conditions of 100 DEG C.
Infusion process is utilized to prepare composite catalyst Mnx-Cey/ Cu-SSZ-13, takes the manganese nitrate of 1.34g and the nitric acid of 0.45g Cerium, is dissolved in a certain amount of deionized water, then the cuprio molecular sieve catalyst Cu-SSZ-13 prepared is added this mixing In solution, magnetic agitation to pasty state, this pasty mixture is dried overnight under the conditions of 100 DEG C, is subsequently placed in Muffle furnace 550 DEG C calcining 4h.MnO in this catalystx、CeO2, the percentage composition of Cu-SSZ-13 be respectively 6%, 4%, 90%.
Step 3, the sample made is sieved just obtain composite catalyst at 8～15MPa pressure lower sheetings, 40～60 mesh Mn-Ce/Cu-SSZ-13。
Comparative example one: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 10%, 0,90% into.
Comparative example two: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 60%, 40%, 0 into.
Comparative example three: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 0,0,100% into.I.e. prepared catalyst is Pure Cu-SSZ-13.
Comparative example four: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 100%, 0,0 into.
Comparative example five: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 0,100%, 0 into.
Embodiment two: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 4%, 6%, 90% into.
Embodiment three: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 8%, 2%, 90% into.
Embodiment four: prepare the low-temperature denitration catalyst Mn that oxide is compound with molecular sievex-Cey/ Cu-SSZ-13, substantially Step with embodiment one, simply MnOx、CeO2, the percentage composition of Cu-SSZ-13 change 2%, 8%, 90% into.
Embodiment five: Mnx-CeyThe application in nitrogen oxides ammonia selective catalysis the reduces of/Cu-SSZ-13 catalyst
By the Mn of preparation in six technical schemes of embodiment one and comparative example one to fivex-Cey/ Cu-SSZ-13 puts into and urges In agent fixed bed reactors, reaction porch: [NO]=500ppm；[NH3]=500ppm；[O2]=3%；N2As balance Gas；Reaction temperature=50～250 DEG C, adjust catalyst height in reaction tube, reaction volume air speed be regulated to 15000h-1.Product nitrogen-oxide analyzer, (MKS, MultiGas 2030HS) carries out on-line analysis.Conversion rate of NOx result is shown in Fig. 1, N2 Selectivity result is shown in that Fig. 2, result show: with MnOx, CeO2, Mn/Cu-SSZ-13 compare, the NH of Mn-Ce/Cu-SSZ-133- SCR performance is optimal, and light-off temperature is 80 DEG C, and in the range of 100 DEG C-200 DEG C, transformation efficiency of the oxides of nitrogen reaches 100%.Compared to MnOx– CeO2The low selectivity of catalyst, the N of Mn-Ce/Cu-SSZ-132Selectivity nearly reaches 100%, it is achieved that real by NOx It is converted into the N of environmental sound2。
By the Mn of four different manganese cerium ratios of preparation in embodiment one to fourx-Cey/ Cu-SSZ-13 is respectively put into catalyst In fixed bed reactors, reaction porch: [NO]=500ppm；[NH3]=500ppm；[O2]=3%；N2As Balance Air；Instead Answer temperature=50～250 DEG C, adjust catalyst height in reaction tube, reaction volume air speed is regulated to 15000h-1.Product On-line analysis is carried out with nitrogen-oxide analyzer, (MKS, MultiGas 2030HS).Conversion rate of NOx result is shown in Fig. 3, N2Selectivity Result is shown in that Fig. 4, result show: work as catalyst activity when the ratio of MnOx, CeO2 is 3:2 optimal.
The Mn that embodiment one is prepared0.06-Ce0.04/Cu-SSZ-13 prepared with in comparative example three pure Cu-SSZ-13 is (i.e. The Cu-SSZ-13 catalyst of one-component) it is respectively put in catalyst fixed bed reactor, reaction porch: [NO]=500ppm； [NH3]=500ppm；[O2]=3%；N2As Balance Air；Reaction temperature=50～250 DEG C, adjust catalyst in reaction tube Height, reaction volume air speed is regulated to 15000,50000,100000h respectively-1(sample that three air speeds are corresponding in turn to is Mn-Ce/Cu-SSZ-13-1,Mn-Ce/Cu-SSZ-13-2,Mn-Ce/Cu-SSZ-13-3).Product nitrogen-oxide analyzer, (MKS, MultiGas 2030HS) carries out on-line analysis.Conversion rate of NOx result is shown in Fig. 5, N2Selectivity result is shown in Fig. 6, result table Bright: composite catalyst Mn0.06-Ce0.04From the point of view of the Cu-SSZ-13 catalyst of/Cu-SSZ-13 and one-component compares, composite catalyzing Agent low temperature active advantage under high-speed is more prominent.Along with the raising of air speed, although selectivity decreases, but still it is maintained at More than 95%.
Although above in conjunction with accompanying drawing, invention has been described, but the invention is not limited in above-mentioned being embodied as Mode, above-mentioned detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art is at this Under the enlightenment of invention, without deviating from the spirit of the invention, it is also possible to make many variations, these belong to the present invention's Within protection.

Claims (5)

1. a composite catalyst for oxide and molecular sieve, is to be main active component with Cu-SSZ-13, with manganese oxide and oxidation Cerium is for playing synergistic active component, and the expression formula of this composite catalyst is Mnx-Cey/ Cu-SSZ-13, wherein: x and y It is molar content 2～8%.
The preparation method of the composite catalyst of oxide and molecular sieve the most according to claim 1, it is characterised in that: include with Lower step:
Step one, use ion exchange or utilize Cu-TEPA to prepare cuprio molecular sieve as template one-step synthesis Catalyst Cu-SSZ-13；
Step 2, infusion process is utilized to prepare composite catalyst Mn-Ce/Cu-SSZ-13:
Take manganese nitrate and cerous nitrate is dissolved in deionized water, the cuprio molecular sieve catalyst Cu-SSZ-that step one is prepared 13 add in this mixed solution, and this pasty mixture is dried overnight under the conditions of 100 DEG C, then, puts by magnetic agitation to pasty state In Muffle furnace, 550 DEG C of calcining 4h, obtain powdery product, MnO in this powdery productx、CeO2, moles the hundred of Cu-SSZ-13 Content is divided to be respectively 2～8%, 2～8%, 90%；
Step 3, powdery product step 2 made sieve be combined at 8～15MPa pressure lower sheetings, 40～60 mesh Catalyst Mnx-Cey/ Cu-SSZ-13, wherein, x and y is molar content 2～8%.
The preparation method of the composite catalyst of oxide and molecular sieve the most according to claim 2, it is characterised in that step one In, use ion exchange to prepare cuprio molecular sieve catalyst Cu-SSZ-13, including: the copper salt solution of preparation 0.1mol/L, will Molecular sieve H-SSZ-13 joins in this copper salt solution, and in oil bath pan, 80 DEG C of constant temperature stirring 2h, then, filter with deionized water Washing, is dried 12h under the conditions of 100 DEG C；Wherein, described acid copper solution be copper nitrate solution, copper-bath, copper chloride solution, One in curpic carbonate solution, basic copper carbonate and basic copper sulfate；The silica alumina ratio of described molecular sieve H-SSZ-13 is 13.6.
The preparation method of the composite catalyst of oxide and molecular sieve the most according to claim 3, it is characterised in that described H- One of preparation following method of employing of SSZ-13:
1) using N, N, N-trimethyl adamantyl ammonium hydroxide is prepared as template；
2) tetraethyl ammonium hydroxide is used to prepare as template；
3) using tetraethyl ammonium hydroxide and N, N, N-trimethyl adamantyl ammonium hydroxide is prepared as mixed templates.
5. the composite catalyst of an oxide and molecular sieve is for low-temperature denitration, it is characterised in that by claim 2 to 4 The composite catalyst that the preparation method of arbitrary described oxide and the composite catalyst of molecular sieve prepares selects to urge for ammonia Changing in nitrogen oxides reduction reaction, reaction temperature is 50～200 DEG C, with ammonia as reducing agent, controls total gas flow rate and exists 300ml/min, air speed is 15000～100000h-1；100-200 DEG C of temperature range purification of nitrogen oxides efficiency be 90～ 100%.
CN201610822968.1A 2016-09-13 2016-09-13 Oxide and molecular sieve compound catalyst and preparation and application thereof Pending CN106311318A (en)

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CN108097301A (en) * 2017-12-14 2018-06-01 中国科学院生态环境研究中心 One kind is used for NH3Composite catalyst of-SCR reactions and its preparation method and application
CN108435237A (en) * 2018-04-08 2018-08-24 中冶京诚工程技术有限公司 A kind of middle low temperature NH3SCR catalyst and the preparation method and application thereof
CN109433254A (en) * 2018-11-09 2019-03-08 大连交通大学 A kind of confinement molecular sieve denitrating catalyst and preparation method thereof
CN109954514A (en) * 2019-03-28 2019-07-02 河北科技大学 It is a kind of for the molecular sieve carried modified manganese-based catalyst and preparation method of exhaust gas from diesel vehicle denitration and application
CN110102337A (en) * 2019-06-06 2019-08-09 安徽纳蓝环保科技有限公司 A kind of preparation method of compound copper-based SCR molecular sieve catalyst
CN110586167A (en) * 2019-09-09 2019-12-20 天津大学 Catalyst for CVOCs catalytic oxidation and preparation method thereof
CN110694670A (en) * 2019-10-22 2020-01-17 天长市润源催化剂有限公司 Preparation method of molecular sieve for purifying diesel vehicle tail gas
CN110721736A (en) * 2019-10-25 2020-01-24 大连理工大学 Preparation method and application of sulfur-resistant composite catalyst for removing nitric oxide in motor vehicle exhaust
CN111250155A (en) * 2020-03-03 2020-06-09 清华大学 Molecular sieve catalyst with double active centers and preparation and application thereof
CN111420704A (en) * 2020-03-31 2020-07-17 包头稀土研究院 Composite catalyst and preparation method and application thereof
CN112246277A (en) * 2020-11-16 2021-01-22 中国科学院宁波城市环境观测研究站 Mn modified Cu-SSZ-13 catalyst and preparation method and application thereof
CN113088697A (en) * 2021-03-25 2021-07-09 洛南环亚源铜业有限公司 Crude copper treatment process and treatment device thereof
CN114602544A (en) * 2022-03-29 2022-06-10 潍柴动力股份有限公司 Modified Cu-CHA molecular sieve composite catalyst and preparation method and application thereof
CN115672390A (en) * 2022-11-09 2023-02-03 沈阳师范大学 MnO (MnO) x Loaded Cu-SSZ-13 molecular sieve composite catalyst, preparation method and application

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